Albumin-conjugated corrole metal complexes: extremely simple yet very efficient biomimetic oxidation systems

An extremely simple biomimetic oxidation system, consisting of mixing metal complexes of amphiphilic corroles with serum albumins, utilizes hydrogen peroxide for asymmetric sulfoxidation in up to 74% ee. The albumin-conjugated manganese corroles also display catalase-like activity, and mechanistic evidence points toward oxidant-coordinated manganese(III) as the prime reaction intermediate.     

Synthesis and analytical properties of micrometric biosensing lipobeads

This paper describes the preparation for the first time of lipobead-based micrometric fluorescence biosensors and the optimization of their analytical properties. The study focused on the well-established urea biosensors as a model system. Fluorescence-sensing lipobeads were prepared by coating carboxyl-functionalized silica microspheres with phospholipids. The enzyme urease and the pH indicator fluorescein-5-thiosemicarbazide were then attached covalently to the phospholipid membrane of the lipobeads. Urease converts urea to ammonia, which results in a pH increase in the analyte solution and to a urea concentration-dependent increase in the fluorescence intensity of the sensing lipobeads. Previous fluorescence-sensing lipobeads were synthesized by coating polystyrene particles with a phospholipid membrane. The membrane was physically attached to the particles and the fluorophores were entrapped in the membrane. In this study, we prepared improved fluorescence-sensing lipobeads by utilizing covalent chemistry to bind the phospholipid membrane to the silica particles and the fluorophores to the membrane. This led to improvement in the stability of the newly developed urea-sensing lipobeads compared to previously developed miniaturized fluorescence biosensors.     

Depth sensing using coherence mapping

A method for depth sensing based on sensing the visibility associated with the coherence function of a laser source is presented. The setup is based on an electronic speckle pattern interferometric (ESPI) setup, where the object depth is encoded into the amplitude of the interference pattern without the need for depth scanning. After performing phase-shifting method, the object three-dimensional (3-D) shape is reconstructed by means as a range image from the visibility of the image set of interferograms and where each gray level represents a given object depth. Experimental results validate the proposed approach for reflective diffuse objects at different measurement distances.     

Iridium corroles

This work reports the synthesis and full characterization of 5,10,15-tris-pentafluorophenylcorrolato-iridium(III) bis-trimethylamine 1 and its octabromo derivative 2. The corrole is planar in both cases (the mean deviation from the plane is as low as 0.0371 A for 1 and 0.0325 A for 2), the UV-vis spectra display a split Soret band with a shoulder attributable to an MLCT transition, and cyclic voltammetry reveals that the iridium(II) oxidation state cannot be accessed, while the oxidation to formal iridium(IV) complexes is achieved at much lower potentials than in other coordination environments.     

Enantiodiscrimination in deuterium NMR spectra of flexible chiral molecules with average axial symmetry dissolved in chiral liquid crystals: the case of tridioxyethylenetriphenylene

Flexible chiral molecules undergoing fast interconversion (on the NMR time scale) between different conformational enantiomers may yield "average" axial species with enantiotopically related sites. Contrary to the situation observed for rigid axial molecules, signals from these enantiotopic sites in NMR spectra recorded in chiral liquid-crystalline solvents can be resolved. In the present work, we studied the deuterium NMR spectra of tridioxyethylenetriphenylene (compound 4) statistically deuterated to 10% in the flexible side chains and dissolved in chiral and achiral lyotropic liquid crystals based on poly(gamma-benzylglutamate). The fast chair-chair flipping of the side chains in 4 on average renders the molecule axially symmetric ( D 3 h ) with pairs of enantiotopic ethylene deuterons. These deuterons exhibit unusually large enantiodiscrimination. To explain this observation, we first describe how the average symmetry of flexible molecules can be derived from the symmetry of the "frozen" conformers and the nature of the averaging process. The procedure is then applied to 4 and used to analyze the NMR results. It is shown that the large enantiodiscrimination in the present case reflects a large difference in the orientational ordering of the conformational enantiomers participating in the interconversion processes as well as a large geometrical factor due to the special shape of the dioxyethylene side groups. (1)H and (13)C NMR spectra of 4 in the same lyotropic liquid crystalline solvent are analyzed to determine its ordering characteristics. Several related cases are also discussed.